Construction material



Oct. 5, 1965 F. E. BERNETT CONSTRUCTION MATERIAL Filed Nov. 15, 1961FIG.

14 FIG-2 FIG. 2a

FIG.3

INVENTOR. FRANK E. BERNETT MORGAN, FINNEGAN, DURHAM 8| PINE ATTORNEYSUnited States Patent 3,209,500 CONSTRUCTION MATERIAL Frank E. Bernett,Yardley, Pa., assignor to Tile Council of America, Inc., New York, N.Y.,a corporation of New York Filed Nov. 13, 1961, Ser. No. 151,660 13Claims. (Cl. 52--309) The present invention relates to new and usefulconstruction materials, and more particularly to improved constructionmaterial comprising a wooden base covered with tile which has unusualstrength and wear resistant properties, and which is highly attractivein appearance.

In low cost housing and other buildings, such as industrial buildings,it is conventional and in fact necessary to employ low grade Wood andcheap synthetic wood products, such as plywood, chip wood, Masonite,Celetex, and the like, for Walling, flooring and other purposes. Lowgrade wood and cheap synthetic wood products, however, are usually notvery attractive. More importantly, such materials usually have poorstrength and wear resistance properties, and thus are not able towithstand severe, high impact industrial type service, or even the heavyduty wear of an ordinary household bathroom floor. Such materials are,however, quite economical, and if they could be adapted to withstandsevere service and to be attractive, they would offer many advantagesover more expensive construction materials.

One possible way of strengthening low grade wood and synthetic woodproducts is to cover them with ceramic tile.

Heretofore, however, there has been no method available for applyingtile, such as ceramic tile, and the like, to wood or wooden products soas to render the resulting construction suitable to withstand severe,high impact, industrial type service.

A difficulty with such a construction in the past has been discovered tobe attributable to the type of mortars and grouts employed to bond thetile to the tile, and the tile to the wood or synthetic wood productsub-surface.

The grouts and mortars previously available included cement compositionsand the so-called organic adhesives.

Cement compositions comprise hydraulic cement, such as Portland cement,sand, and other additives to improve bond strength, settingcharacteristics, and the like. Such compositions are hard and brittleand cannot endure the strain of movement and impact, concomitant, forexample, with heavy use of floors.

The so-called organic adhesives are solvent systems with rubber or resinbinders and inert fillers. One of the leading products of this type onthe market today is sold under the trade name CTA12, by Minnesota Miningand Manufacturing Company.

The organic adhesives are slow to develop strength, are not strong inbond when dried, shrink excessively, and have poor water resistance.They are designed to maintain a large degree of flexibility to offsettheir inherently low bond strengths. Their flexibility is so great,however, that when used to set tile on wooden substrata, no structuraladvantage is gained from the layer of tile because stress cannot betransmitted through the adhesive layer. The flexible, weak organicadhesives do not support the tile well enough to prevent cracking andchipping of tile under heavy use. Field and laboratory observation haveproven the very poor performance of tile installations of this kind onwood when impact loads are prevalent, such as rolling loads on small orhard wheels and Womens high heels of small bearing area. All of thesedisadvantages render such material unsuitable for the type ofconstruction being discussed.

Another difliculty of equal or more serious consequence has been theproblem of maintaining proper joints in a tile or a similar surface overwood at the joints between wood pieces. Movement between separate woodpieces from thermal or moisture expansion and contraction or frombuilding movement induce concentrated stresses in the tile or similarmaterial layer at the wood joint locations causing dam-age to the tileor similar material. The only method to prevent this happening, in thepast, has been to use expansion joints over the wood joints. Expansionjoints are unsightly, however, and pose many difiiculties if they are tofunction properly. In the past, even the most perfect method of bondingtile to wood was susceptible to failure when extended from one piece ofwood to another without expansion joints or similar means.

It is an object of the present invention to provide methods forinstalling ceramic tile on wood or wood products in such a manner as toprovide a tile surface more durable than has heretofore been consideredpossible over wood or wood products.

Another object of the present invention is to provide methods forinstalling ceramic tile on wood or wood products which increases theload bearing capacity of the wood by significant factors and whichproduces new and improved floor installations, having unexpectedly highwear resistance properties.

Still another object of the present invention is to provide methods forinstalling ceramic tiles on wood or wood products with thin bed adhesivelayers which are both strong and flexible, and which contain percentsolids at the time of application and thereafter.

A further object of the present invention is to provide a method ofinstalling ceramic tile on wood or wood product substrata whilesimultaneously cementing individual pieces of the substrata together toprevent movement at joints between the pieces of the Wood substrata, andto eliminate the need for expansion joints in the tile layer.

Still a further object of the present invention is to provide methodsfor installing impermeable components to wood or wood products in orderto provide a tough continuous vapor barrier over the wood surfaces.

An additional object of the present invention is to provide methods forinstalling ceramic tile or similar material to wood or wood products,including chipboard, Masonite iand =Celotex type 'board to form aprotective skin and vapor barrier over the wood substrata, and in orderto add significantly to the strength of the board, and to enhance itsbeauty and durability.

Still another object of the present invention is to provide new methodsfor the installation of ceramic tile or similar material to wood andwood products which is particularly suitable for floor surfaces.

Still another object of the present invention is the provision of newand improved construction materials which comprise a wood or woodproduct substrata having superimposed thereon and bonded thereto ceramictile, the resulting construction material having improved properties ofstrength and durability.

Another object of the present invention is to provide a method ofinstalling ceramic tile on counter tops directly on wood surfaces whichwill impart higher impact strength to the tile than has heretofore beenpossible so that dropping of heavy objects such as pots and crockery onthe counter top will not crack and chip the tile, thereby avoidingunsightly and unsanitary conditions.

Another object of the present invention is to provide an improved methodof applying ceramic tile to wood panels which enhances the panelsstructurally and decoratively, and more particularly, improve theirimpact resistance, moisture sensitivity and flexural strength. Theresulting panels are suitable for use as curtain walls, wall PatentedOct. 5, 1965 surfacing board, counter tops and the like, where woodalone is wholly or partly objectionable.

Another object of this invention is to provide a method for installingceramic tile so that the finished installationbis(2-hydroxy-3,4-epoxybutoxy) benzene,

(2-hydroxy-4,S-epoxypentoxy) benzene.

Among the preferred epoxides are the epoxy polyethers of polyhydricphenols obtained by reacting a polyhydric 1,4-bis and will have thedurability, under heavy service, of convenphenol with a halogencontaining epoxide or dihalohydrin tional all-masonry installationswithout the high degree in the presence of an alkaline medium.Polyhydric of resilience of all-masonry installations which arerephenols that can be used for this purpose include, among portgd to b;tirilizg and hlarmfifil t;) the legsdof fpeople others,1 resorcirllol,clatecholll, h){dIOqUllI11OI16,2H6lt)h} (l4lifS- stan mg an wa mg on tem or ong perio s 0 time. orcino or po ynuc ear p eno s, suc as is yiThe methods and construction materials disclosed 1Q droxyphenyl) propane(Bis-phenol A), 2,2-bis(4-hyherein are especially suitable for use inflooring. Flooring droxyphenyl) butane, 4,4-dihydroxybenzophenone, hisproduced according to the teachings contained herein is(b-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl) far superior towooden flooring alone. The new and pentane, and1,5-dihydroxynaphthalene. The halogennovel constructions and methodsincorporate a grouted containing epoxides may be further exemplified by3- joint between the tile and other components which is chloro-l,2-epoxybutane, 3-bromo-1, Z-epoxyhexan 3- strong, flexible andresilient; able to absorb impact withch1oro-1,2-epoxyoctane, and thelike. O Causing damage to the tiles; able to absorb bending of Themonomer products produced by this method from theflsurfajce wtithcglltcausingt damage to {hi tiles. d gihykdric pheriofls andl epichlorohydrinmay be represented ccor mg 0 e presen invcn 10H, 1 as con 1syt e generaormu a: covered that new and useful flooring constructions can 0 be madeby bonding ceramic tiles to wooden substrata with epoxy resin, whichupon curing, has certain char- CHT (3H CH20TR O CH2 CHCH acteristics.wherein R represents a divalent hydrocarbon radical of the f Thecharlacteristics of the cured epoxynresin (suitable dihygric phenlol.Th? polylmerlic firoducltls l:vill generallly or use in t e presentinvention are as fo ows: 1) virnot e a slnge simpe mo ecu e ut w1 e acomp ex tually no shrinkage; (2) a relatively high compressive mixtureof glycidyl polyethers of the general formula: strength, which is atleast, or in excess of 3000 psi; (3) O 0 an elastic modulus of at least005x10 and preferably 6 at least 0.5 10 (4) a tensile strength at least/5 of the H'CH'O(RO'CH"CHOHCH"O)ll-043E? ctfmpressive gtr ength; andf(5)a bond strength tocergmlc 3 wherein R is a divalent hydrocarbon radicalof the n e i g m eXwSF O measured i g dihydric phenol and n is aninteger of the series 0, l, 2, A O t 636 Properties t e cured epoxy resmm t Z 3, etc. While for any single molecule of the polyether 12 9 ofmagmtuges, mdlcatFd are l i for goo is an integer, the fact that theobtained polyether is a mixper zrmalrice of :1 e lhnstlzllllla h,Partlcu arly preveillt ture of compounds causes the determined value forn to rea un er 1g 0a to g' c t 3 be an average which is not necessarilyzero or a whole 6 f i etwien number. The polyethers may in some casescontain a g i {in o i f 8 on aween very small amount of material withone or both of the W 18 essenfila 0 g llncrease Strengt 0 t e terminalglycidyl radicals in hydrated form. 3 1 Over t 9: h The aforedescribedglycidyl polyethers of the dihydric f a e 3. 3? phenols may be preparedby reacting the required proven ionf anb1 alvr e piopelrdies tisc ose derelna tg ortions of the dihydric phenol and the epichlorohydn'n i pre5?. y t tpercen .5; 1 Sys an i er in an alkaline medium. The desiredalkalinity is obtained i I Sys W1 i ar i by adding basic substances,such as sodium or potassium i jg gz g i fit t a a 52 hydroxide,preferably in stoichiometric excess to the epiactivatedeb g g g t if 23i chlorohydrin. The reaction is preferably accomplished at y e y Va a 6P0 ar temperatures within the range of from C. to 150 C. llqllldS, suchas water, alcohol, and the hke. Th

e heating is contmued for several hours to effect the g The resinousepoxides suitable for use in the present reaction and the roducti thenWashed free of alt and invention comprise those compounds having thereactive base p S S 0 50 epoxy resm roup 0 These epoxide reslns areavailable 1n several forms varying from a viscous liquid to a solidresin. Especially suitable are those resins which are liquid or neartheir The polyepoxides may be saturated or unsaturated, alisofteningPoint at room temperature phatic, cycloaliphatic, or heterocyclic andmay be subyp of the P Y resins which y be p y stituted if desired withsubstituents such as chlorine are the ePiChIOTOhYdTiIPhiS-PheHOI p Soldunder the atoms, hydroxyl groups, ether radicals and the like. T heytrademarks P Resins (Shell Chemical Corporation), "may also be monomericor polymeric, Gen Epoxy (General Mills), DER Resins (Ciba), Examples ofthe polyepoxides include, among others, L Resins (Bakelite Corporation),P (John epoxidized glycerol dioleate, 1,4-bis(2,3-epoxypropoxy) Dabney);the peracetic acid-epoxidized compounds sold tzgrgzene,1,3-bis(ij-gpoliryprlopozg) lie'lie l'lfi 34,4'-bis lildertlfit(r:ademark)UngX lgiepotides (linion Carbide -epoxypropoxy 1p eny e er,1s -epoxyemic ompany an t e tri uncti'ona epoxy comprop oxy)-octane,1,4-bis(2,3-epoxypropoxy) cyclohexpounds sold under the trademarkEpiphen (The Borden ane, 4,4-bis(2-hydroxy 3,4'-epoxybutoxy) diphenyldi-Company). An example of the trifunctional type of methylmethane,1,3-bis(4,5 epoxypentoxy)-5-chlorobenmp unds is pip en Which has thefollow" zene, 1,4-bis(3,4-epoxybutoxy)-2-chlorocyclohexane, 1,3- ingformula:

H H H O OCH 0 OCH O C o o -o-oH H H H2 where n is a number such thatfrom about 180 to 200 grams of the resin contain about one gram mole ofepoxide group.

The epoxide resins suitable for use in the present invention may containbetween about 5 and 400 percent, and preferably between about and 300percent, by Weight, based on the weight of epoxy resin, of an inert,finely divided solid.

Suitable finely divided inert solid materials for use with the epoxyresins include fillers, such as asbestos, albality, silica, mica, flintpowder, quartz, kryolite, Portland cement, limestone, atomized alumina,barytes, talc, pyrophyllite, various clays, diatornaceous earth, andother like materials. Also may be mentioned pigments, such as titaniumdioxide, cadmium red, carbon black, aluminum powder, and the like.

Suitable other colorants may be added to the epoxy resin if desired.Typical of these are: National Fast Red (National Aniline); CalcoCondensation Green A.Y. (American Cyanamid); Calco Condensation Blue(American Cyanamid); Bismark Brown (National Aniline); Blue Lake (13%Ponsal Blue, 10% aluminum hydrate and 77% blanc fixe), Krebs BP-l79-D,Blue Lake Krebs BP-258-D, Lithol Tower, Chrome Yellow, Iron Blue, MilariBlue, Monastral Green, Maroon Toner, Chrome Green, Chrome Orange, IronOxide Reds, Aluminum Powder, and flatting agents like diatomaceoussilica and silica aerogel. The color materials should be selected,however, so as to be non-reactive with the epoxy resins and otheringredients at atmospheric temperature, as otherwise this might causepoor storage stability and also affect the retention of adhesiveness.

The finely divided inert solid materials suitable for use herein mayhave an average particle size ranging between about 50 mesh and 400mesh, and preferably between about 100 and 400 mesh (U.S. Std. Series).The exact size of the inert finely divided solid materials will dependupon the particular application of the compositions.

In addition to finely divided solid materials, a wide variety ofresinous modifiers may be added to the epoxy resin systems disclosedherein. Among these may be mentioned the phenolic resins, such asaniline formaldehyde resins; urea resins, such as urea formaldehyderesins; melamine resins, such as melamine formaldehyde resins; polyesterresins, such as those produced from polybasic acids and polyhydroxylalcohols and which may contain free carboxyl groups and/or aliphatichydroxyls capable of reacting with the epoxy resins; vinyl resins suchas vinyl chloride, vinylidene chloride and the like; and polystyrene.The addition of such resinous modifiers is well understood in the art.The resinous modifiers may vary from about 1 to about 100 percent ormore, by weight, based on the weight of the epoxy resin.

An especially suitable resinous modifier for use in the presentinvention is polystyrene resin, and this resinous modifier is preferred.The polystyrene resin should vary from about 10 to about 50 percent, andpreferably from about 20 to 40 percent, by weight, based on the weightof the epoxy resin. Polystyrene resin, it has been discovered,considerably enhances the flexibility of the bonds produced with theepoxy resin compositions disclosed herein.

The epoxy resins may also have incorporated therein, if desired, alubricant, such as silicone oils, silicone jelly, petroleum jellies, andso forth. As an example of the silicone oil may be mentionedorgano-siloxane liquid supplied by General Eelectric Company as SiliconeLiquid No. 81069. Any of the commercially available silicone jellieswhich are sold under a wide variety of trademarks and trade names may beused.

Typical of the curing or cross-linking agents for epoxy resins may bementioned the amine curing agents, i.e., amines containing at least 1and preferably at least 2 amino nitrogen atoms, e.g., polyamines. Suchmaterials include ethylene amine, ethylene diamine, propylene diamine,diethylene triamine, dipropylene triamine, tri ethylene tetramine,tripropylene tetramine, tetraethylene pentamine, tetrapropylenepentamine, and mixtures of the foregoing. Also may be mentioned higheralkyl polyamines, such as alkyl polyamines in which the alkyl group isbutyl, hexyl, 'octyl, and so forth.

Due to their greater availability, commercially produced polyfunctionalamines may also be used as hardeners. Examples of such commerciallyavailable amines are those obtained from the Chemical Division of Armour& Company under the trade names Duomeen O and Duomeen S. Duorneen 0consists essentially of a mixture of N alkyl trimethylene diaminesderived from technical grade oleic acid. The alkyl group content isdistributed as follows:

Duomeen S consists essentially of a mixture of N-alkyl trimethylenediamines derived from soya acids. The alkyl group content is distributedapproximately as follows:

Percent Preferred curing or cross-linking agents for the epoxy resincompositions used in the present invention may be described aspoly-amido-amine epoxide hardeners. Epoxy resins cured with suchhardeners, it has been discovered, have the unique and and unexpectedproperty of being water soluble. Additionally, and very importantly,epoxy resins cured with such hardeners have the physical propertiesdescribed hereinabove and are therefore suitable for use in theconstruction materials of the present invention.

The poly-amido-amine epoxide hardeners are produced by copolymerizationof polyamines with polycarboxylic acids, the copolymerization reactionbeing permitted to proceed to such an extent that the products producedare soluble in both epoxy resin and water.

In conducting the copolymerization reaction, it is important that excesspolyamine be used, so that unreacted polyamine is present in theresulting copolymer. In the case where no unreacted amine remains, watersolubility is lost and the products do not possess the required abilityto harden an epoxide polymer. Nor are such reaction products soluble inthe epoxy resin and Water.

Suitable amine hardeners are prepared by reacting the polyamines andpolycarboxylic acids described herein at temperatures below thedecomposition temperature of the polyamines by employing the appropriatepolyamine in stoichiometric excess of that theoretically required toreact with the appropriate polycarboxylic acid. The temperature of thereaction is preferably between about and 200 C. Especially good resultsare achieved when the temperature is between about and C.

Aliphatic polyamines containing two or more amino nitrogens may be usedto produce such poly-amido-amine hardeners. Polyamines containingprimary nitrogens are especially suitable.

Polyamines suitable for making the poly-amido-amine compounds disclosedherein have the formulae:

where R is a hydrocarbon radical and n is an integer having a value ofat least 2, and preferably between about 4 and 10. Such polyaminesshould have a formula weight of at least 60 and preferably between about90 and 500.

Examples of polyamines that may be used to produce such hardenersinclude ethylene diamine, propylene diamine, diethylene triamine,dipropylene triamine, triethylene tetramine, tripropylene tetramine,tetraethylene pentamine, tetrapropylene pentamine, and mixtures of theforegoing. Also may be mentioned higher alkyl polyamines satisfying theabove formulae, such as alkyl polyamines in which the alkyl group isbutyl, hexyl, octyl and so forth. The hydrocarbon radical R attached tothe amino nitrogen atoms may have up to 50 carbon atoms or more.Preferably, however, the hydrocarbon radical has fewer than about 30carbon atoms.

Especially suitable are polyamines which have a value of n of at least4, or polyamines wherein the formula weight of R is greater than about90. It has been found that where polyamines are used in which n is aninteger less than 4, or R is of a molecular weight lower than 90,satisfactory hardening action is not obtained. This is believed to bedue in part to the reaction of such low molecular weight polyamines withpolycarboxylic acids to form compounds having a high melting point,which compounds require high reaction temperatures, e.g., above thedecomposition temperature of the polyamines, to effect the fusion whichprecedes the amidation reaction. The same problems are experienced when,for example, a polycarboxylic acid, e.g., R(COOH) is employed wherein Ris of low molecular weight. A further difficulty found to exist when lowmolecular weight polyamines and polycarboxylic acids are used is thatthe reaction products produced are insoluble in epoxide polymers andtherefore are not able to function as hardeners.

The polycarboxylic acids suitable for reaction with the above describedpolyamines to produce poly-amido-amine epoxide hardeners have at leasttwo carboxyl groups and may be represented by the formula R(COOH) whereR is a hydrocarbon radical which may be saturated or unsaturated,aliphatic, cyclicaliphatic, or heterocyclic, and n is an integer havinga value of at least 2. Among the preferred polycarboxylic acids are thestraight chained saturated dicarboxylic acids such as adipic, pimelic,suberic, azeloic, sebacic, nonone dicarboxylic acid, and the highermembers of this series, including mixtures thereof. Also may bementioned the straight chained unsaturated dicarboxylic acids, includingcitiraconic acid, mesaconic acid and itaconic acid. Especially suitablefor use are the socalled resin acids. These may be classified asditerpene acids, a major constituent being abietic acid. When suchditerpene acids are dimerized, a dicarboxylic acid results. Particularlyuseful are those diterpene acids which, upon being dimerized, have aformula weight of about 300 to 900, and preferably between about 500 to600.

The poly-amido-amine epoxide hardeners are produced by dissolving thepolycarboxylic acid and polyamine in a suitable organic solvent, inwhich the polyamine and the polycarboxylic acid are soluble. The amountof the polyamine is in excess of that stoichiometrically required toreact with the polycarboxylic acid. The amount of excess polyamine ispreferably at least about 5 percent, and may be between about 5 and 200percent, or higher, and preferably between about 50 and 150 percent,based on the polycarboxylic acid. The solvent employed is not critical,since after mixing the solvent is preferably removed, for example, byevaporation. The residue remaining after solvent evaporation is thenheated to a temperature of between about 100 to 200 C., care being takenthat the temperature employed is below the decomposition temperature ofthe polyamine used. The time of heating should be at least aboutone-half hour, or between about 1 and 25 hours, and is preferablybetween about 1 and 16 hours. Although the solvent is preferably removedprior to heating, it should be understood that the solvent may also beremoved after heating.

When liquid epoxide resin compositions are used, the adhesivecompositions may be produced by simply dissolving the hardener in theliquid epoxide resin. When the epoxide resin is solid, the epoxide resinmay be dissolved in a suitable solvent prior to the addition of the ohardening agents. Suitable solvents which dissolve the epoxide resinsinclude phenyl glycidyl ether, acetone, methyl ethyl ketone, isophoroneethyl acetate, butyl acetate, ether alcohols such as methyl, ethyl orbutyl ether of ethylene glycol, and so forth.

Specific examples embodying epoxy resin systems cured by thepoly-amido-amine agents disclosed hereinabove and preferred for use inmaking the improved construction materials of the present invention areas follows:

EXAMPLE 1 The prime poly-amido-amine hardener was prepared by dissolving14.6 parts by weight of adipic acid in parts by weight of ethyl alcoholand to this mixture were added 40.0 weight parts of N-octadecenetrimethylene diamine. After solution was effected, the resulting mixturewas heated to evaporate the alcohol, then placed for 16 hours in an ovenheld at C. Upon cooling an orange-brown paste was obtained. This wasslowly soluble in an equal weight of water yielding a gelatinoussolution.

The epoxide polymer used was of the epichlorohydrinbisphenol of acetonetype, having a viscosity of about 13,000 centipoises (25 C.), an epoxideequivalent of approximately 200, and a melting point in the range of 8to 1 2 C. The epoxide polymer was a complex mixture of glycidylpolyether and had the following general formula:

The orange-brown paste produced was added to an equal weight of theliquid epoxide polymer described hereinabove. An adhesive compositionwhich hardened on standing was obtained.

The adhesive composition was effectively and readily hardened in thepresence of water, and was capable of being readily removed fromsurfaces upon application of a water-soaked cloth.

EXAMPLE 2 As a comparison for Example 1, an adhesive composition wasprepared by dissolving N-octadecene trimethylene diamine in an equalweight of the liquid epoxy resin polymer described in Example 1. Theresulting composition did not readily or effectively harden in thepresence of water and aqueous alkali and acid solutions. Nor was itremovable from a surface by application of a watersoaked cloth.

EXAMPLE 3 As a comparison for Example 1, and following the procedure ofExample 1, stoichiometric amounts of dimerized tall oil resin werereacted with the following amines by heating at C. for 1 hour:

Ethylene diamine Diethylene triamine Tetraethylene pentamine N-alkyl (Ctrimethylene diamine The products of these reactions were added to anequal weight of the liquid epoxide resin described in Example 1. Theresulting adhesive compositions did not effectively harden, and did notexhibit the water-cleanability characteristic of the adhesivecompositions of Example 1.

EXAMPLE 4 Example 3 was repeated, except that in preparing the aminehardener, the amines were added to the dimerized tall oil resins in anamount which was 100 percent in excess of that stoichiometricallyrequired to react with the dimerized tall oil.

When added to the liquid epoxide resin of Example 1, water-cleanablecompositions were obtained which readily and effectively hardened.

9 EXAMPLE EXAMPLE 6 The procedure of Example 1 was followed but withsubstitution of a solid epoxide polymer of the epichlorohydrin-bisphenolof acetone type. The solid epoxide resin was dissolved in phenylglycidyl ether, at a 4:1 IfiSlIlCCthCI ratio. The epoxide polymer had amelting point of about 42 C. and an epoxide equivalent weight of 500.The resulting composition had properties similar to those obtained inExample 1.

EXAMPLE 7 weight parts of sebacic acid were dissolved in 385 parts ofethyl alcohol and to this were added 17.8 weight parts of Duomeen S, aproduct of the Armour Company. The Duomeen S consisted of a mixture ofN- alkyl trimethylene diamines derived from technical grade soya acids.The alkyl group content was distributed as follows:

Percent C 2 This solution was then heated to evaporate the alcohol andthen heated at 155 C. for 2 hours. The soft resinous product obtainedwas dissolved in an equal weight of liquid epoxide polymer of the typedescribed in Example 1, and the resulting composition exhibited the samewatercleanability and good-hardening characteristics as the adhesivecomposition produced in Example 1.

EXAMPLE 8 A resin base and pigment hardening composition were preparedusing the following formulae:

The resin base:

28.9 weight parts epoxide resin 14.3 weight parts titanium dioxidepigment 11.4 weight parts polystyrene resin 45.4 weight parts blanc fixePigment-hardener composition:

28.0 weight parts amido-amino tall oil resin 1.7 weight parts diethylenetriamine 68.5 weight parts blanc fixe 1.8 weight parts silica aerogelThe epoxide resin used was of the epichlorohydrinbisphenol of acetonetype descirbed in Example 1. The amide-amino tall oil resin was thatproduced in Example 4 by the reaction of dimerized tall oil with excesstetraethylene pentamine at a temperature of 155 C.

The resin base and pigment-hardener composition were mixed, and asmooth, white, easily spreadable composition was produced.

EXAMPLE 9 The following resin-base was prepared:

63.5 weight parts of epoxide resin 5.5 weight parts of phenyl glycidylether 1.3 weight parts (2.2 bis(-hydroxyphenyl)propane) 26.7 weightparts of polystyrene resin 3.0 weight parts of petroleum jelly 10 andmixed with 3.33 times its weight of the following filler-hardenercomposition:

11.2 weight parts amido-amino tall oil resin, equivalent weight of 135,viscosity at 25 C. of 250 centipoises 0.25 weight parts diethylenetriamine 85.6 weight parts sand (through 30 mesh screen) 2.8 weightparts silica aerogel .05 Weight parts carbon black The epoxide resin wasof the solid type described in Example 6. It had an epoxide equivalentof about 500, a viscosity of approximately 7,000 centipoises (25 C.),and a melting point of about 42 C.

The poly-amido-amino tall oil resin was produced according to theprocedure of Example 4 by reacting dimerized tall oil resin with percentexcess tetraethylene pentamine (based upon the stoichiometric amount ofa tall oil resin), at a temperature of 155 C.

This gave a trowellable composition that was used to set ceramic quarrytiles on a wooden substrata and to subsequently fill the joints betweenthese. Excess material was removed from the tile face by mopping with asponge wet with water. Hard, adherent, chemically resistant bonds andjoints were obtained.

The epoxy resin systems of Examples Sand 9 may be improved, if desired,by addition of a small amount of water to the filled epoxy resincomponent, i.e., the epoxy resin plus fillers and pigments, prior to theaddition of the hardening agent. The addition of water produces agel-like structure in the composition which is extremely stable onstorage, and, when the resulting epoxy resin is hardened, an epoxy resinadhesive is produced which has improved flow and sag properties, whencompared to similar compositions to which water has not been added. Theamount of water added may vary from about 0.5 to 15 percent, based uponthe weight of epoxide resin.

The following example illustrates an epoxy resin adhesive system towhich water has been added to the filled epoxy resin portion to gel theepoxy resin prior to addi tion of the hardening agent.

EXAMPLE 10 The prime poly-amido-amine hardener was prepared bydissolving 14.6 parts by weight of adipic acid in 100 parts by weight ofethyl alcohol and to this mixture were added 40.0 weight parts ofN-octadecene trimethylene diamine. After solution ,WaS effected, theresulting mixture was heated to evaporate the alcohol, then placed for16 hours in an oven held at C. Upon cooling an orange-brown paste wasobtained. This was slowly soluble in an equal weight of water yielding agelatinous solution.

A resin base and pigment-hardener composition were prepared.

The resin base had the following composition:

Percent by weight The pigment-hardener composition had the followingcomposition:

Percent by weight Poly-amido-amine hardener 31.90 Ti0 8.62 Blanc fixe45.69 Silica (325 mesh) 13.79

The epoxide resin used was the same as that described in Example 6. Thepoly-amido-amine epoxide hardener was that prepared in this example,supra.

1.5 parts by weight of the resin base were mixed with 1.0 parts byweight of the pigment-hardener composition, and a smooth, easilyspreadable composition was produced. The composition was spread over awooden surface and glazed ceramic tiles in spaced relation laid thereon.The joints between the tiles were filled by spreading more of thecomposition over the tiles, thus filling the joints. Excess material wasremoved from the face of the tiles by Scraping with a trowel edge andthen wiped clean with a water-soaked cotton cloth. Hard, impermeablebonds and joints were thus obtained. The composition exhibited extremelygood flow resistance and non-sagging properties in the joints.

In addition to two-part systems, all powder one-part epoxy systems mayalso be used to prepare epoxy resin adhesive compositions suitable foruse in the present invention.

A suitable one-part dry, 100 percent solid epoxy resin system for use inthe present invention comprises an epoxy resin of the type describedherein, an acid salt of a polyamine and a strong base. At the time ofuse, a polar liquid, such as water, alcohol, and the like, is added tothe dry mix to initiate polymerization,

The mechanism and sequence of events which take place when the liquid isadded to the dry composition are believed to be as follows:

7 Liquid+base+acid salt of polyamine gives:

(a) Solution of base-l-solution of acid salt of polyamine;

(b) Solution of base+solution of acid salt of polyamine gives a freeamine-I-water;

(c) Free amine-l-epoxide compound gives epoxide polymer.

In Step (at) the addition of sufficient liquid transforms the drypowdery mixture to a fluid form as well as dissolving the base and theacid salt of the polyamine. The solution of these two products causesthem to react according to Step (b) to yield' the free amine. Finallythe free amine reacts with the epoxide monomer or prepolymer as shown inStep (c) forming the cross-linked to the mechanism set forth above, butit is believed to be the probable description of the chemical processinvolved.

The polyamine acid salts may be prepared by reacting suitable polyamineswith organic or inorganic acids, such as hydrochloric, sulfuric, nitric,phosphoric, acetic, formic, and the like. The polyamines suitable foruse are those indicated above in connection with the polyamido-amineepoxide hardeners.

'Strong bases include the alkali and alkaline earth metal hydroxides,although sodium and potassium hydroxide are preferred.

The use of silica aerogel and finely divided sand in combination ascarrier and aggregate for the components of the one-part, all powderepoxy systems under discussion serves two functions. These materialsinsure the availability of a great surface on which the cross-linking ofthe epoxide resins and the amine hardeners will take place. The sandmoderates the speed of reaction by taking up a considerable amount ofthe exothermal heat produced by the initial solution of some of thecomponents and the heat produced during the cross-linking of the amineand epoxide resin. When the balance is changed in 'favor of greateramounts of aerogel the curing rate is increased due to the greateramount of heat available to the reaction but shrinkage of thecomposition is increased also. A balance between rate of curing epoxidepolymer. We do not wish to restrict ourselves and ultimate shrinkage maybe obtained by varying the amounts of filler in the form of aggregateand carrier which are included in the dry compositions.

Liquid epoxide resins and liquid amine hardeners in salt form throughadsorption on the aerogel and sand are made substantially dry and can becontacted with each other without initiating any appreciable degree ofpolymerization. The mixtures are relatively uniform and therefore may beprepared in such manner that any portion may be removed from the wholeand still retain substantially the proportion of epoxide resin and aminehardener which were originally determined to be most suitable for theparticular ingredients used in making up the dry composition.

Compositions of the type described will, if exposed to unduly greatamounts of water, partially react but this quality is not such that itwould be proper to characterize the compositions as water-sensitive.Their sensitivity to water in the form of humidity or other vapor liesbetween Portland cement and calcium chloride. The compositions thereforemay be shipped in plastic-lined paper bags and the like without otherspecial precautions being necessary.

Specific examples of one-part, percent solid epoxy resin compositionshaving the properties described hereinabove are given in the followingexamples:

EXAMPLE 11 The hydrochloric acid salt of diethylene triamine wasprepared by mixing 129 weight parts of 37 percent bydr-ochloric acidwith 45 weight parts of diethylene triamine, dissolved in 200 weightparts of water. The water was evaporated from this solution by drying atC. and a crystalline salt residue obtained.

100 weight parts of a liquid epoxide resin were mixed with 233 parts ofa fine, 100 mesh, silica sand and 40 parts of silicon dioxide aerogel.The epoxide resin was of the epichlorohydrin-bisphenol of acetone type,having a viscosity, of about 22,000 centipoises, an epoxide equivalentof approximately 200, and a melting point in the range of 8 to 12 C. Itsstructural formula is represented as:

The silicon dioxide aerogel had a particle size in the range of 0.5 to3.0 microns and a specific surface area of about 200 square meters/gram. The function of the addition of the sand which may have a particlesize between 16 and 300 mesh and silicon dioxide aerogel is that ofconverting the liquid polymer into the form of freefiowing powder.

The following powder mixture was prepared:

15 weight parts of the acid salt prepared above 373 weight parts of theresin powder prepared above 8.4 weight parts of powdered sodiumhydroxide This composition yielded a free-flowing powder, remarkablystable upon long-term storage, even though comprising acidic and basicconstituents in intimate contact with one another. When 92 weight partsof water were added to this powder a fluid, coherent mix was obtained.This was troweled onto a wooden floor surface, at a thickness ofapproximately 75 and used (as a setting bed-adhesive) for ceramic tile.After a period of 24 hours the material had hardened and a strong bonddeveloped to the wooden surface and the underside of the tile.

EXAMPLE 12 The hydrochloric acid salt of N-octadecene trimethylenediamine was prepared by reaction of 42 weight parts 13 of 37%hydrochloric acid with 84.4 Weight parts of the diamine. The N-oleictrimethylene diamine is prepared by the reaction of octadecyl amine,derived from oleic acid, with acrylonitrile and subsequentlyhydrogenating this product. Its structural formula is represented asfollows:

62.3 weight parts of the acid salt 36.3 weight parts of the resin powder1.4 weight parts of sodium hydroxide This composition yielded a fine,free-flowing powder, which subsequently required 16.5 percent of itstotal weight of water to give a fluid composition. This con1- positionwas used as a jointing compound, placed between the edges of tile bondedto a wooden floor. EX- ceptional ease in cleaning excess material fromthe tile faces was noted and hard, chemically resistant joints wereobtained.

when mixed with 16.2% of its weight of water gave a fluid composition,suitable for use as a chemically resistant setting bed or jointingcompound for ceramic tile on wooden surfaces. This material showedrelatively early development of hardness. The epoxide resin referred toin this example was of the polyfunctional type, and contained onegram-mole of epoxide group per 180 to 200 grams of resin.

EXAMPLE 14 The following composition (based on weight):

Percent Epoxide resin of Example 11 19.5 Titanium dioxide 8.0 Silicondioxide aerogel 9.7 Hydrochloric acid salt of N-octadecadiene diamine18.3

Wollastonite 300 mesh) -I: 40.0 Powdered sodium hydroxide 4.5

when mixed with 28% of its weight of Water gave a creamy, non-granular,white, fluid composition suitable for use to set and grout ceramic tileon wooden surfaces.

EXAMPLE 15 The following composition (based on weight):

Percent Hydrochloric salt of Duomeen O '6.2 Epoxide resin of Example 118.4 Silicon dioxide aerogel 4.2 Powdered sodium hydroxide 1.3 Fine sand79.9

14 mixed with 16 percent of its weight by water gave a smooth, viscouspaste composition which developed a strong resistant bond between a woodsubstrata and ceramic tiles which was substantially set at the end of 24hours.

EXAMPLE 16 The following composition (based on weight):

Percent Hydrochloric salt of Duomeen S 6.2 Epoxide resin of Example 1'17.5 Silicon dioxide aerogel 3.2 Powdered sodium hydroxide 3.0

Fine sand 80.1

mixed with 15% of its weight by water resulted in an excellent settingand grouting composition for adhering tiles to wooden substrata andshowed a minimum of contraction upon hardening.

Such further dry, all-powder one-part mixes suitable for use in thepresent invention comprise an epoxy resin 'and a complex amine hardenerproduced by the reaction of a metal salt and a diamine or polyamine. Atthe time of use, a suitable polar liquid, such as water, alcohol, and soforth, is added to the dry mix to activate the hardener and cure theepoxy resin to produce epoxy resin adhesive compositions having theproperties described above, and suitable for use in making the new andnovel construction materials disclosed herein.

Suitable dior poly-amines for making the complex amine salts which serveas hardeners in the one-part epoxy systems under discussion have beendescribed here inabove in connection with the poly-amido-aminehardeners.

The metal salts suitable for use in preparing the hardeners of thesystems under discussion are those capable of releasing cations whichform stable complexes with amines. Typical of these are the strong andweak mineral and organic acid salts of calcium, zinc, copper, silver,and nickel. Of these, exceptionally good results are achieved withcalcium and zinc salts and these are preferred. The anions of the saltsare not critical. For example, the halides, nitrates, sulfates,phosphates, acetates, and other weak and strong mineral and organic acidsalts of these metals may be employed, as will be readily apparent tothose skilled in the art.

In preparing the hardeners, the metal salts capable of yielding cationswhich react with amino groups to form stable complexes are added,preferably in finely divided form, to the polyamines describedhereinabove, and the mixture is agitated. The time of reaction andtemperature will depend upon the particular polyamine and metal saltsused. Completion of the reaction is indicated by disappearance of thepolyamine and the appearance of powder in those cases where the reactionis conducted below the melting point of the reaction product. When thereaction is conducted above the melting point of the reaction product,the reaction is continued until a homogeneous mixture appears, at whichtime the reaction product may be cooled to below its melting point togive a solid material which may be pulverized to a powder. In thoseinstances Where the complex aminate reaction product is a liquid, thismay be suitably absorbed on a carrier, as will be explained more fullyhereinbelow.

Illustrative of the amine complex compounds which serve as hardeners forthe one-part epoxy system now under discussion are those produced whencalcium chloride is reacted with ethylene diamine. This reaction may beillustrated as follows:

15 More realistically, the reaction product has probably a continuouscrystalline structure represented as:

Cl-P]I H 11 1 01-1? 11 H 1'1 01 5ca++1 I 5 Ca++N N-E Ca c1- 11 u H H c1-rt 11 n it c1- and extending, of course, in three dimensions. As can beseen, the complex hardeners may be described as stable amine complexesof metal salts and polyamines. The structures of other stable aminecomplexes will readily suggest themselves to one skilled in the art fromthe foregoing description.

The complex inorganic salt-polyamine hardeners may be mixed withepoxy-type polymers or monomers of the liquid or solid type describedhereinabove.

In the epoxy resin systems under discussion, suitable fillers andpigments may be added, as has already been described hereinabove.

In forming epoxy resin bonding compositions from onepart systemscontaining the complex inorganic salt-polyamine hardening agents, enoughof the hardeners are added to the epoxy resin composition to insure thatupon activation, good hardening is achieved. Preferably the hardenersand epoxy-resin prepolymers are present in the dry compositions instoichiometric proportions. Depending on the nature of the adhesivecomposition desired, however, greater or lesser amounts of the hardenermay, of course, be used.

When water or other polar solvents are added to the compositions to makethem functional, -i.e., to initiate and cause polymerization, it isbelieved that a hydrate, alcoholate or other similar complexes of themetal salt portion of the aminate hardener are formed, therebydisplacing the free amine, which is then available for reaction andhardening of the epoxide resin. Although not wishing to be restricted tothe description set forth above, it is believed to be the probabledescription of the chemical process involved.

Specific examples of all-powder, one-part epoxy systems containing thecomplex inorganic salt-polyamine hardeners disclosed are given in thefollowing examples:

EXAMPLE 17 An amine complex A of calcium chloride and ethylene diaminewas prepared by mixing 55.5 parts by weight of anhydrous, finelypowdered calcium chloride with 30.0 parts by weight of diamine at roomtemperature. The mixture was agitated to form an intimate dispersion.Agitation was continued until the liquid phase disappeared and a drypowder which was somewhat caked appeared. The temperature of the mixtureat the commencement of agitation increased rapidly, indicating thatreaction was occurring, and fell gradually as the powder formed and theliquid phase disappeared. The molar ratio of CaCl to ethylene diaminewas 121, so that the reaction product corresponded to the empiricalformula 15.4 grams of the product thus obtained were dispersed in 100grams of liquid epoxy resin of the epichlorohydrin-bisphenol of acetonetype, having a viscosity of about 130 poises (25 C.), an epoxideequivalent of about 200, and a melting point in the range of about 812C.

To this dispersion, there were then added 9.7 grams of water, thisweight being that stoichiometrically required for formation of the CaCl.H O hydrate. During mixing the odor of ethylene diamine was evident,and after 24 hours, the mass had solidified.

EXAMPLE 18 100 weight parts of the liquid epoxy resin described inExample 17 were mixed with 233 parts by weight of fine sand and 40 partsby weight of silicon dioxide aerogel. The silica dioxide aerogel had aparticle size in the range of 0.5 to 3.0 microns and a specific surfacearea of 200 square meters per gram. The function of the addition of thesand, which had a particle size between about 16 and 300 mesh, and thesilica aerogel is that of converting the liquid polymers into the formof a free-flowing powder.

The following powder mixture is prepared:

15 weight parts of the complex amine A of Example 17. 373 weight partsof the resin powder prepared above.

The resulting mixture was a free-flowing powder, remarkable stable uponlong term storage, even though the epoxy resin and hardener were inintimate contact with one another.

When water is added to this powder a fluid, coherent mix was obtained.This mix is spread onto a wooden floor surface at a thickness ofapproximately and used as a setting bed for ceramic tile. After a periodof 24 hours the material hardens and a strong bond developed between thewooden surface and the underside of the tile.

EXAMPLE 19 A composition similar to that described in Example 17 wasprepared, but using 34.5 grams of diethylene triamine in place of the30.0 grams of ethylene diamine in Example 17. Comparable results wereobtained.

EXAMPLE 20 Example 17 was repeated, with the exception that 37.5 gramsof tetraethylene pentamine were used in place of the 30.0 grams ofethylene diamine of Example 17. Comparable results were obtained.

Although specific forms of epoxy resin systems have been described foruse in the present invention, it should be understood that other epoxyresins having the physical properties described hereinabove may also beused.

The method of installing ceramic tile on wood or wood products to givethe improved constructions disclosed herein is as follows:

The wood is nailed, or otherwise held in position, as it would be innormal construction practices, except that open joints are left betweenboards, sheets, or planks. The width of the joint can be from to /2",but A to /4" is a more practical range for approximately /2" thickboards. All joints are backed by joists, studs, cats, subflooring, orsheeting. The epoxy resin adhesive as disclosed hereinabove is preparedand floated over the area to be filed or otherwise covered withcomponent surfacing material, and forced into the open joints betweenboards. The adhesive is gauged by drawing a notched trowel through thefloated layer and removing excess adhesive if there is any. The tile, orother surfacing material is laid on the troweled adhesive and fixed inplace to form a level and true surface. After a proper curing time,usually twenty-four hours, an epoxy resin adhesive similar tom the sameas the mortar adhesive, but in any event possessing the propertiesdisclosed hereinabove, is forced between the tile or component surfacingmaterial to fill the joints and be level with the finished floorsurface. The cured installation thus achieved meets all the claims ofthis invention.

The method of installing ceramic tile or other component surfacingmaterial on old wood installations is similar. New boards may or may notbe applied to the old wood surface depending on the condition of the oldwood surface. When old wood is to be directly covered, the adhesive isapplied as a thin float coat and forced into all openings in the oldwood surface. The procedure 1 7 from that point on is the same as fornew wood surface as described previously.

The thickness of the adhesive used is not restricted except from apractical viewpoint. Thickness from A to A" have proven equallysatisfactory in performance tests.

The following examples illustrate the method of preparing the newconstruction materials disclosed herein and the unexpected propertiesthereof. Although specific, it should be understood that these examplesare not intended to restrict the scope of the present invention, exceptas such limitations may appear in the claims.

EXAMPLE 2 1 Fir plywood thick was applied over 2" wide joists spaced 16"on center. Resin coated nails were used every 8" on the studs. Joints inthe plywood layer were left open A". The adhesive composition preparedaccording to Example 9 was forced between the plywood sheets in the A"open joint, and spread on the plywood surface with a A square notchedtrowel, giving an average mortar thickness of Square edge porcelainceramic tile, 1 /2" x 1 /2", premounted with paper on the face of 1' x2' sheets were laid on the mortar and beat to level. After twenty-fourhours, the paper was removed from the face of the tile and the sameadhesive composition was applied to the tile surface and forced into thejoints between the tiles. Excess epoxy resin adhesive composition wascleaned from the tile surface with a sponge wetted by plain water. Thecured floor section was tested for strength and durability after sevendays aging.

As a comparison, another installation was produced using the sametechnique, with the exception that a mortar prepared from organicadhesive was substituted for the epoxy resin adhesive composition.

In tests performed simultaneously on the two constructed panels, thepanels were subjected to three hours of heavy rubber wheel traflic andthree hours of steel wheel traflic in that order, using a Robinson FloorTester.

The tile installation with the epoxy resin adhesive of Example 9survived the entire test with practically no damage. Only minor chips attile edges occurred which were not visible at from the floor surface.There were no structural damage.

The installation laid and grouted with organic adhesive was severelydamaged at the end of rubber wheel test and was completely destroyedafter ten minutes of steel wheel traflic.

EXAMPLE 22 Example 21 is a repeated with the exception that 2" x 2"cushion edged, natural clay ceramic tile premounted with paper on theface of 1 x 2' sheets are substituted for the poreclaim ceramic tile ofExample 21. Similar results are obtained.

EXAMPLE 23 Example 21 was repeated with the exception that 4%" x 4%cushion edged, glazed adsorptive ceramic tile laid singly, weresubstituted for the porcelain ceramic tile of Example 21. Similarresults were obtained.

EXAMPLE 24 Example 21 was repeated with the exception that 6" x 6" x /2"and 6" x 3" x /2 red quarry tile, laid singly, were substituted for theporcelain ceramic tile of Example 21. Similar results were obtained.

EXAMPLE 25 Floor panels prepared according to Example 21 and using thetile disclosed therein, and various bonding materials were prepared andtested for impact resistance. The results of the tests are indicated inTable I.

The data in Table I were obtained by dropping a 2" diameter steel ballonto the firmly seated tile installations. As is readily apparent, theamount of impact that can be withstood by the construction of thepresent invention (Panel 1) is considerably higher than that that couldbe withstood by Panels 2 and 3.

EXAMPLE 26 A 4' x 4' floor was installed by laying plywood on woodenjoints. The flooring was divided into four equal sections, and coveredwith 1 /2" square poreclain, square edged title following the procedureof Example 21, and

using the bonding materials specified in Table H.

Table II Mortar Grout Quadrant No. 1--. Epoxy resin adhesive of Epxoyresin adhesive of Example 9. Example 9. Quadrant No. 2 PO; Sand.Quadrant No.3- PC: Sand. Quadrant N0. 4. Epoxy resin adhesive of Example9.

In Table I and II, CTA-12 refers to the organic adhesive referred tohereinabove and supplied by Minnesota Mining and Manufacturing Co.

After permitting the floor to stand for 7 days, it was tested with aRobinson Floor Tester.

The test schedule was as follows: 1 hour of rubber wheel traffic with aload of lbs. per wheel; 1 hour of rubber wheel traffic with a load oflbs. per wheel; 1 hour of rubber wheel traffic with a load of 240 lbs.per wheel. A repeat of the above with steel wheels substituted for therubber wheels.

The only quadrant to survive the entire rubber wheel test was quadrantNo. 1 which used the epoxy resin adhesive of Example 9 for both layingand grouting the tile. There was absolutely no damage to this area.

In quadrant No. 2 the Portland cementzsand grout was partially destroyedby the flexing action of the floor. No tile was damaged.

In quadrant No. 3 the grout in the wheel path was com pletely destroyed(powdered). No tile Was damaged.

In quadrant No. 4 with CTA-12 adhesive and the epoxy resin of Example 9used as a grout, the tile were broken at the edges (first damage notedduring the first hour). The strong grout exerted such unyieldingpressure on the tile as the plywood flexed that the tile flaked, orspalled, at many joints.

The most interesting observation made was that the tile set with theepoxy resin adhesive of Example 9 reinforced the plywood sufliciently tocut the deflection between joints in half for that quadrant. Thus, theepoxy resin set and grouted quadrant No. 1 flexed less than half theamount that quadrant No. 4 did.

The condition of each quadrant after one hour of steel wheels with aload of 80 lbs. and one-half hour of steel wheels with a load of 160lbs. was as follows:

Quadrant No. 1.Al1 grout and all tile were intact. Some tile showedflaws at corners which were the beginning of vertical cracks through thetile. No tile or grout was loose or pitted.

19 Quadrant N0. 2.Tl1e Portland cementzsand grout was powdered in alljoints in the wheel path. Tile edges were crumbled and powdered so thatjoints between tiles were to A" wide. No tile was cracked and the bondto Tests made for joint strength and tile damage at joints have provedthis method to be superior to that in which tight joints with or withoutreinforcing is employed.

The preferred assembly provides a continuous floor the epoxy resinadhesive was intact. layer which will not permit localized movement todamage Quadrant N0. 3.Tile and grout in the wheel path the tile surface.were completely disintegrated. Plywood showed through The advantages ofusing the preferred type of comin most parts and the surface veneer onthe plywood was struction are shown in the following example: cut andsplintered. E

Quadrant N0. 4.The tile was all broken into small M pieces, with manypieces dislodged. The epoxy resin lj p t were made of 3 W1de P y P 5/8grout was almost perfectly intact forming a grid between thick lollltedIn the ({entef thlr lfingth, and covered on h k il pieces, one side withceramic mosaic t1le installed following the procedures of Example 21,and using the adhesive pre- EXAMPLE 27 pared according to Example 9.Three different joint con- Flooring constructions produced according tothe prostructions were used. The assemblies were strained incedure ofExample 21 were prepared and tested for tentionally along thelongitudinal axes until failure ocstrength. For comparison purposes,various bonding macurred. The results of the tests are tabulated belowin terials were used, as indicated in Table III. Table IV. The jointconstruction in each of the test The thickness of the plywood used inthe tests Was /8". 2() panels is described in the ,table. The ultimatetension The results of these tests are summarized in Table III. force inTable III is an average of 4 runs.

Table III Construction details Load deflection Deflection Mortarconstant at failure Grout type (lbs/in.) (in.)

Thickness Type Control (Plain Thick plywood.-- 1,050 0.33

is no tile).

%2 UTA-12 PCzSand 1,000 0.35 Epoxy resin 1,051 0.39 do 2, 900 0. 3,1000.38 3,900 0. 4,000 0. 31 4,000 0. 34 4,500 0.30 5,000 0. 35 4,900 0. 35

l Epoxy resin produced according to Example 9.

2 Epoxy resin produced according to Example 10.

In Table III, load deflection constants are listed for Table IV variouscombinations of mortar, grout, tile and plywood.

The data were obtained using 3" wide samples with tile Ultimate appliedas noted in the table. The tiles were porcelain Test coflstrmtlml gi figceramic tile, 1% square, square edged, thick. The 0 test specimens wereloaded at their mid-point and sup- 1 Pl 1) tt 1 d t, ddl im 91 ported onknife edges 16 apart. The deflection was wi ood l ih ti mm m e 0 e 0measured at the mid-point of the ample 2 Plain u plywood j tile jointover 454 The data in Table III is suflicient to calculate actual 3 Steelfly screen over plain butt joint, mid- 1,026 capacities of a floorinstalled y the techniques disclosed 4 ,33,;gg ggggg gzggggg g joint, me760 herein and usmg epoxy resin mortars and grouts having 1 joint overwood joint. the properties described. The calculations, on the basis 5gg gggg gfif glf fi g g fi g1%? 21205 of supported spans between oints16 on center (the most 1 epoxy resin adhesive. conservativeconsideration) indicates that flooring pro- 6 g fi gg f g y fzifi ducedaccording to the teachings contained herein have epoxy resin adhesive.

a maximum deflection of 0.0075" when the floor is loaded at 200 poundsper sq. ft. The calculation for a concentrated load is more approximate.It indicates less than The preferred method of constructing thefioorings dedeflection for a 200 pound concentrated load at a scribedherein using a plywood substrata was used in Test point mid-way betweenoists. I Nos. 5 and 6. The ultimate tension force for the joint Ininstalling ceramic tile on plywood according to the construction ofTests 5 and 6 is considerably higher than teachings of the presentinvention, it has found to be adthe ultimate tension strength for jointconstructions of vantageous to employ a special but simple constructionTests 1 to 4, inclusive, as will readily be apparent from technique.Table IV.

The plywood sheets are assembled with A" to A2" The invention will befurther clarified byareading of the wide open joints between them. Theseopen joints are following description in conjunction with the drawing,then filled with the epoxy resin adhesive compositions in which: of thetype disclosed herein or at the time the adhesive FIG. 1 is a verticalsection, partially broken away, compositions are being applied to thefloor surfaces to throughawooden floor having ceramic tile bondedthereto receive the tile. with the epoxy resin disclosed herein;

FIG. 2 is a cross section of the flooring of the preferred embodiment ofthe present invention, showing the pieces of wood with spaced joints;

FIG. 3 is a cross section of a flooring having a construction slightlydifferent from that shown in FIG. 2.

As shown in FIG. 1, a wooden floor 2 is overlaid with an epoxy resinadhesive composition 4 and ceramic tile 6. The adhesive resincomposition bonds the ceramic tile to the wooden substrata. The spacesbetween the tile are also filled with epoxy resin 8.

FIG. 2 shows a preferred embodiment of the present invention in whichpieces of the wooden floor, such as plywood 12, are laid with wide openjoints 14 between them. The epoxy resin composition 16 covers theflooring and fills the open joints between the boards. The ceramic tile20 is laid over the wooden joint with the middle of the tile bridgingthe joints. Epoxy resin also fills the joints 22 between the tiles.

FIGURE 2(a) shows a section of the FIGURE 2 embodiment taken through ajoist 30 which supports wooden pieces 12.

FIG. 3 shows a construction which is the same as that in FIG. 2 with theexception that the ceramic tiles are laid such that the tile joint isover the Wood joint.

EXAMPLE 29 This example illustrates a three-part epoxy resin systemwhich may be used in the present invention. The following resin-base wasprepared:

63.5 weight parts of epoxide resin 26.7 weight parts of polystyreneresin 5.5 weight parts of phenyl glycidyl ether 1.3 weight parts of(2,2' bis(-hydroxyphenyl) propane) and mixed with the following hardenerportion:

37.3 weight parts amide-amino tall oil resin, equivalent weight of 135,viscosity at 25 C. of 250 centipoises. 1.2 weight parts diethylenetriamine.

After thorough mixing was added the following filler portion whichyielded a trowelable material:

285.0 weight parts sand (through 30 mesh screen) 9.3 weight parts silicaaerogel .15 wei ht parts carbon black The epoxide resin was of theepichlorohydrin bisphenol of acetone type described in Example 1.

The resulting adhesive was used in place of the adhesive of Example 9 inthe tests reported in Examples 21 and 26. Similar results were obtained.

EXAMPLE 30 Table V Percent rebound of Construction Construction detailsglass marble after free fall 1 Tile set and granted with epoxy resin 27of Example 9 on thick plywood. 2 Tile set and grouted with (ETA-12 on 28thick plywood. 3 Tile set and grouted conventionally in 87 Portlandcement.

Based on the performance cited elsewhere in this application of ceramictile installed in epoxy thin-set on plywood, on the Robinson FloorTester, one would expect the resiliency of the assembly of construction1 of Table V to be very high. In other words, one would expect a ceramicor glass marble when dropped on such a surface to rebound without losingmuch of its kinetic energy to the tile. When a glass marble is droppedon a conventional assembly, i.e., construction 3 of Table V, it reboundsto nearly the same height from which it was dropped and if not deflectedwill continue to bounce several times. If the same marble is dropped ona soft carpet, for example, it does not bounce but stops dead becauseall the kinetic energy is absorbed. Likewise, if it is dropped on aceramic tile floor installed by an organic adhesive such as CTA-12,i.e., construction 2 of Table V, it rebounds very little or not at all.This is because the kinetic energy is absorbed and dissipated in theadhesive or other members. The floor does not have the elastic capacityto keep the kinetic energy in the bouncing marble. So, while the ceramictile installed by the epoxy has the durability of ceramic tile installedin the conventional way by Portland cement, it lacks the elasticresiliency shown by this system; On the other hand, and this is mostsurprising and was unexpected, it absorbs impact energy very similar tothe manner of ceramic tile installations using organic adhesives. Ofcourse, as shown elsewhere, organic adhesive installed tile lacksdurability on the Robinson Floor Tester, as has already been shown.

The invention in its broader aspects is not limited to the specificmethods, compositions and constructions described, but departures may bemade therefrom within the scope of the accompanying claims withoutdeparting from the principles of the invention and without sacrificingits chief advantages.

What is claimed:

1. An improved structural member comprising wood and ceramic tile incombination, and having enhanced load bearing capacity, wear resistance,and impact resistance, said member comprising a plurality of woodenpieces aligned in spaced relationship so as to leave spacestherebetween; means adjacent one surface of said wooden pieces forsupporting said pieces and maintaining them in aligned spacedrelationship; a cured epoxy resin mortar bed covering a second surfaceof said wooden pieces and extending into and filling the spacestherebetween; and a plurality of ceramic tile pieces set in said curedepoxy resin mortar bed in spaced edge to edge relationship and bonded tothe wooden pieces thereby; said ceramic tile pieces having grout betweentheir edges; said cured epoxy resin mortar bed being formed by curing anepoxy resin adhesive composition which comprises a resinous epoxidecharacterized by a reactive group; between about 5 and 400 percent byweight, based upon the weight of resinous epoxide, of an inert, finelydivided filler having an average particle size ranging between about 5and 500 mesh; and an epoxy resin hardener capable of entering into across-linking reaction with the resinous epoxide to cure and harden thesame; said cured epoxy resin mortar bed having a compressive stress ofat least 3000 p.s.i.; an elastic modulus of at least 005x10 a tensilestrength at least /5 of the compressive strength and being substantiallynon-shrinking; and forming a bond between the wooden boards and theceramic tile which has a strength in excess of 400 psi. measured asshear.

2. The improved structural member of claim 1 wherein the epoxy resinhardener is an amino amide formed by reacting a polyamine compound witha carboxylic acid compound.

3. The structural member of claim 1 wherein the grout between the edgesof the ceramic tile pieces is a cured epoxy resin adhesive composition.

4. The improved structural member of claim 1 wherein the ceramic tilesstraddle the spaces between the wooden pieces.

5. The improved structural member of claim 1 wherein the spaces betweenthe tile are over the spaces between the wooden pieces.

6. The improved structural member of claim 1 wherein the resinousepoxide comprises between about 0.5 and 15 percent water, based upon theweight of the resinous epoxide.

7. The improved structural member of claim 1 wherein the hardenercomprises a dry mixture of an acid salt of a polyfunctional amine and astrong base, the dry mixture being activatable upon addition of a polarsolvent.

8. The improved structural member of claim 1 wherein the hardenercomprises a dry mixture of a stable amine complex of a metal salt and apolyamine, the salt having a cation capable of forming a stable complexwith an amino group.

9. The method of claim 1 wherein the cured epoxy resin has an elasticmodulus of at least 0.5 X10 10. The method of enhancing the load bearingcapacity, wear resistance, and impact resistance of a structural membercomprising, in combination, ceramic tile and wood, which comprises:preparing a wooden substrata by aligning a plurality of wooden pieces inspaced relationship on a plurality of support members so that the woodenpieces straddle the support members; covering the wooden pieces with amortar bed of an epoxy resin adhesive composition, the epoxy resinadhesive composition extending into and filling the spaces between thewooden pieces; said adhesive composition comprising: a resinous epoxidecharacterized by a reactive group; between about and 400 percent byweight, based upon the weight of resinous epoxide, of an inert, finelydivided filler having an average particle size ranging between about 5and 500 mesh; and an epoxy resin hardener capable of entering into across-linking reaction with the resinous epoxide to cure and harden thesame; setting a plurality of ceramic tile pieces in the mortar bed inspaced edge to edge relationship; grouting the spaces between theceramic tile pieces; and allowing the mortar bed to harden, to therebyprovide a bond strength between the wooden pieces and the ceramic tilein excess of 400 psi. measured as shear; the epoxy resin adhesiveemployed being such that the cured resin has a compressive stress of atleast 3000 p.s.i.; an elastic modulus of at least 0.05 X 10 a tensilestrength at least /s of the compressive strength; and beingsubstantially non-shrinking.

11. The method of claim 10 wherein the ceramic tiles are laid so as tostraddle the spaces between the wooden pieces.

12. The method of claim 10 wherein the ceramic tiles are laid so thatspaces between the tiles are over the spaces between the wooden pieces.

13. The method of claim 10 including the step of filling the spacesbetween the tile with an epoxy resin adhesive.

References Cited by the Examiner UNITED STATES PATENTS 1,649,890 11/27Cederquist 5 2-389 1,913,031 6/33 Kertes 52-392 1,953,337 4/34 Carson94-15 2,705,223 3/55 Renfrew 260-18 2,718,829 9/55 Seymour 52-3902,738,825 3/56 McElroy 52-389 2,741,909 4/ 5 6 Hartlmair 52-3 842,897,179 7/59 Shechter 260-47 2,899,397 8/59 Aelony 260-18 2,970,124 1/61 Drummond 52-390 3,002,941 10/61 Peterson 260-18 3,045,396 7/62 Matyas52-389 3,050,493 8/62 Wagner 260-37 FOREIGN PATENTS 523,607 1953Belgium.

OTHER REFERENCES Paint Oil and Chemical Review, November 9, 1950, page15.

Progressive Architecture, August 1959, page 139.

FRANK L. ABBOTT, Primary Examiner.

WILLIAM I. MUSHAKE, JACOB L. NACKENOFF,

Examiners.

1. AN IMPROVED STRUCTURAL MEMBER COMPRISING WOOD AND CERAMIC TILE INCOMBINATION, AND HAVING ENHANCED LOAD BEARING CAPACITY, WEAR RESISTANCE,AND IMPACT RESISTANCE, SAID MEMBER COMPRISING A PLURALITY OF WOODENPIECES ALIGNED IN SPACED RELATIONSHIP SO AS TO LEAVE SPACESTHEREBETWEEN; MEANS ADJACENT ONE SURFACE OF SAID WOODEN PIECES FORSUPPORTING SAID PIECES AND MAINTAINING THEM IN ALIGNED SPACEDRELATIONSHIP; A CURRENT EPOXY RESIN MORTAR BED COVERING A SECOND SURFACEOF SAID WOODEN PIECES AND EXTENDING INTO AND FILLING THE SPACESTHEREBETWEEN; AND A PLURALITY OF CERAMIC TILE PIECES SET IN SAID CUREDEPOXY RESIN MORTAR BED IN SPACED EDGE TO EDGE RELATIONSHIP AND BONDED TOTHE WOODEN PIECES THEREBY; SAID CERAMIC TILE PIECES HAVING GROUT BETWEENTHEIR EDGES; SAID CURED EPOXY RESIN MORTAR BED BEING FORMED BY CURING ANEPOXY RESIN ADHESIVE COMPOSITION WHICH COMPRISES A RESINOUS EPOXIDECHARACTERIZED BY A REACTIVE -(OXIRAN-2,3-YLENE)GROUP; BETWEEN ABOUT 5AND 400 PERCENT BY WEIGHT, BASED UPON THE WEIGHT OF RESINOUS EPOXIDE, OFAN INERT, FINELY DIVIDED FILLER HAVING AN AVERAGE PARTICLE SIZE RANGINGBETWEEN ABOUT 5 AND 500 MESH; AND AN EPOXY RESIN HARDENER CAPABLE OFENTERING INTO A CROSS-LINKING REACTION WITH THE RESINUOUS EPOXIDE TO ANDHARDEN THE SAME; SAID CURED EPOXY RESIN MORTAR BED HAVING A COMPRESSIVESTRESS OF AT LEAST 3000 P.S.I.; AN ELASTIC MODULUS OF AT LEAST0.05X10**6; A TENSILE STRENGTH AT LEAST 1/5 OF COMPRESSIVE STRENGTH ANDBEING SUBSTANTIALLY NON-SHRINKING; AND FORMING A BOND BETWEEN THE WOODENBOARDS AND THE CERAMIC TILE WHICH HAS A STRENGTH IN EXCESS OF 400 P.S.I.MEASURED AS SHEAR.